CN109019703B - Plasma enhanced oxidation roasting method for high-nickel cathode material of lithium ion battery - Google Patents
Plasma enhanced oxidation roasting method for high-nickel cathode material of lithium ion battery Download PDFInfo
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- CN109019703B CN109019703B CN201811073203.8A CN201811073203A CN109019703B CN 109019703 B CN109019703 B CN 109019703B CN 201811073203 A CN201811073203 A CN 201811073203A CN 109019703 B CN109019703 B CN 109019703B
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a method for strengthening oxidizing roasting of a high-nickel anode material of a lithium ion battery, which is characterized in that a precursor and lithium source powder are uniformly mixed and placed in a roasting device for roasting, oxygen-containing gas is continuously introduced, and the oxygen-containing gas generates active oxygen with positive charges through plasma discharge to synthesize the high-nickel anode material. The method has important significance for improving the comprehensive performance of the high-nickel anode material, and particularly has obvious effects of reducing the cation mixing degree of the high-nickel anode material, improving the cycle performance and the rate capability of the material, reducing the alkalinity of the material and improving the processing performance of the material.
Description
The application is a divisional application. The original patent numbers are: 201710380474.7, filing date: the invention is named as follows on 25 days of 2017, 05 and 25 months: a plasma reinforced oxidizing roasting method of a high-nickel anode material of a lithium ion battery.
Technical Field
The invention belongs to the technical field of energy material preparation, and particularly relates to a plasma enhanced oxidation roasting method of a high-nickel anode material of a lithium ion battery.
Background
With the rapid development of portable electronic products, new energy automobiles and other related industries, the market demand of lithium ion batteries is rapidly increased, and the demand of positive electrode materials is also rapidly increased.
The high nickel cathode material generally refers to a layered cathode material with relatively high nickel content, and comprises ternary lithium nickel cobalt manganese (622 type, 701515 type, 811 type and the like according to the proportion of nickel cobalt manganese), lithium nickel cobalt aluminate NCA and various doped and modified materials with various formulas. The high nickel material has the advantages of higher specific capacity and energy density, and the material with higher nickel content has more outstanding advantages, so the high nickel material is considered to be an ideal positive electrode material of the high-energy-density lithium ion battery.
The conditions for synthesizing the high nickel cathode material are severe, and one important reason is that Ni is generated during the roasting reaction2+Is relatively difficult to be completely oxidized into Ni3+Resulting in partial Ni2+And Li+Generating mixed row, a small amount of Ni2+Occupy Li+The position of (2) can seriously affect the electrochemical performance of the material, and cause the reduction of specific capacity, the deterioration of cycle performance and the reduction of rate capability.
To promote Ni2+The oxidation of (2) reduces the degree of ionic mixing, and generally requires the introduction of pure oxygen (O) during the calcination2). This, on the one hand, increases the costs of oxygen production and places high demands on the oxidation resistance of the furnace. Meanwhile, because the activity of oxygen is not strong enough, only a small part of pure oxygen really participates in the oxidation, and most white emission is lost. Ni is not sufficiently active even when fired under pure oxygen atmosphere2+Can not be completely oxidized, the problem of ion mixing and discharging is not completely solved, and the further improvement of the electrochemical performance of the material is restricted. The lithium carbonate can decompose carbon dioxide during roasting, has certain reducibility and is not beneficial to Ni2+And thus lithium hydroxide rather than lithium carbonate is required for the preparation of the high nickel material. Lithium hydroxide is more costly than lithium carbonate and is odorous and corrosive, resulting in harsh worker labor conditions and severely shortened sagger life.
Considering ozone (O) at normal temperature3) The oxidation ability of Ni is very strong, and people have connected an ozone generator to a furnace for synthesizing high-nickel materials, and then let ozone into the furnace, trying to promote Ni by using the strong oxidation property of ozone2+But the effect is not significant. Probably due to O2And O3Are neutral molecules and have little difference in oxidation capacity at high temperature.
Another method for reducing the degree of ionic mixing is to adopt a lithium-rich formula, namely, an excessive lithium source (excessive 10-15%) is added in the process of proportioning, and Li is added+In a large excess to suppress Ni2+In Li+The occupancy of the bits. The method has certain effect, but the defect is obvious. Firstly, an excessive amount of lithium source is added, resulting in increased cost; secondly, excessive lithium remains in the cathode material, which leads to the enhancement of the alkalinity of the material and the deterioration of the subsequent processing performance. The remaining lithium is usually removed by subsequent processes such as water washing, which not only wastes time and labor, but also causes deterioration of material properties. In addition, the residual lithium compound is not electrochemically active, which also results in a reduction in the specific capacity of the material. The material with high lithium proportion has lower specific capacity, better cycle performance and rate capability; the material with low lithium proportion has higher specific capacity, but has poorer cycle performance and rate capability. Therefore, it is not an ideal method to use a lithium-rich formulation.
Low temperature plasma chemistry is an emerging discipline that has developed over the 60's of the 20 th century based on the interdigitation of physics, chemistry, electronics, vacuum technology, and the like. The plasma technology can make the substance realize a series of new chemical reactions which can not be realized by the traditional chemistry by absorbing electric energy. The plasma gas discharge space contains abundant highly excited molecules, atoms and ions, and special chemical reactions can be carried out by utilizing the highly active groups, so that the plasma gas discharge space has completely different unique rules from the traditional chemical method.
There is a report in the literature on an atmospheric pressure flat-plate plasma reactor in which an oxygen-containing gas is introduced, and the oxygen-containing gas generates a large amount of oxygen-reactive particles including atomic O and ozone O under plasma discharge3Isoneutrals of O+、O2 +、O3 +Isopositively charged particles, and O2 -Etc. negatively charged particles, etc. When the plasma is introduced into water, hydroxyl radicals (. OH) are generated, and the plasma has strong oxidizing property and fast oxidizing speed. The plasma can be used for water treatmentTo rapidly oxidize and decompose almost all biomacromolecules, organic matters and inorganic matters and finally degrade the biomacromolecules, the organic matters and the inorganic matters into CO2、H2O and inorganic salt, and develops a kind of advanced oxidation technology on the basis of the O and the inorganic salt, and the O and the inorganic salt are applied to the fields of advanced oxidation treatment of ship ballast water, advanced oxidation treatment of domestic drinking water and the like.
At present, the technology is not applied to the field of preparation of high-nickel cathode materials of lithium ion batteries to solve the problem of Ni during roasting of the high-nickel cathode materials of the lithium ion batteries2+The document reports that sufficient oxidation is difficult to cause defects of high cation-rearrangement degree.
Disclosure of Invention
The invention aims to solve the technical problem of providing a plasma enhanced oxidation roasting method of a lithium ion battery anode material, overcoming the defect that Ni is generated when a high-nickel anode material of a lithium ion battery is roasted2+The difficulty of sufficient oxidation results in a defect of high cation-rearrangement degree. The invention improves the comprehensive performance of the high-nickel anode material.
The technical means adopted by the invention for solving the technical problems is as follows:
a method for strengthening oxidizing roasting of a high-nickel anode material of a lithium ion battery is characterized in that a precursor and lithium source powder are uniformly mixed and placed in a roasting device for roasting, oxygen-containing gas is continuously introduced, and the oxygen-containing gas generates active oxygen with positive charges through plasma discharge to synthesize the high-nickel anode material.
Preferably, the roasting device is a quartz tube furnace; more preferably, the firing apparatus is a temperature-programmed quartz tube furnace.
Further, the method for strengthening, oxidizing and roasting the high-nickel cathode material of the lithium ion battery comprises the following steps:
(1) uniformly mixing the precursor and the lithium source powder, and placing the mixture in the quartz tube furnace connected with an atmospheric pressure discharge plasma generating device;
(2) introducing the oxygen-containing gas into the quartz tube furnace, discharging the gas after reaction from the quartz tube furnace, and keeping the gas pressure in the furnace at normal pressure in the reaction process;
(3) adjusting the voltage, frequency and power of the atmospheric pressure discharge plasma generating device to enable the oxygen-containing gas to generate plasma discharge in the quartz tube furnace to generate active oxygen;
(4) heating the quartz tube furnace, and performing heat preservation roasting to synthesize the high-nickel anode material of the lithium ion battery;
(5) and after the baking and sintering, closing the atmospheric pressure discharge plasma generating device after the furnace temperature is reduced to be below 150 ℃.
Preferably, in the step (1), the lithium source is one or both of lithium hydroxide and lithium carbonate.
Preferably, in the step (2), the oxygen-containing gas is air, oxygen-enriched air or pure oxygen, and the flow rate is 0.05-5L/min.
Preferably, in the step (3), the atmospheric pressure discharge plasma generating device adopts an alternating current power supply or a pulse power supply, the voltage is 10-50 kV, the frequency is 1-50 kHz, and the power is 100-1000W.
Preferably, in the step (4), the heating rate is 100-400 ℃/h, the heat preservation temperature is 700-900 ℃, and the roasting time is 4-48 h.
In the technical scheme, when the step (4) is baked with heat preservation, active oxygen generated by plasma discharge effectively strengthens the oxidation of nickel and the solid-phase reaction of the precursor and the lithium source.
Preferably, in the step (4), the lithium ion battery high-nickel cathode material is LiNixM1-xO2Wherein x is more than or equal to 1.0 and more than or equal to 0.6, M is one or more of Co, Mn, Al, Mg, Ti, V, Cr, Fe, Cu, Zn, Sr, Y and Zr, including but not limited to LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.90Co0.05Mn0.05O2、LiNi0.80Co0.15Al0.05O2。
In one embodiment, the high nickel cathode material of the lithium ion battery is nickel-cobalt lithium aluminate (molecular formula LiNi)0.80Co0.15Al0.05O2Abbreviated as NCA).
The invention also adopts the following technical scheme to solve the technical problems:
a plasma strengthening oxidizing roasting device for synthesizing a high-nickel anode material of a lithium ion battery comprises a quartz tube furnace and an atmospheric pressure discharge plasma generating device; the quartz tube furnace comprises a quartz tube, an air inlet pipe and an air outlet pipe, wherein the air inlet pipe is positioned at one end of the quartz tube; the atmospheric pressure discharge plasma generating device comprises a high-voltage power supply and an atmospheric pressure discharge plasma generator arranged in the quartz tube furnace.
Further, the quartz tube is arranged in a quartz tube type hearth, and the quartz tube type hearth is provided with a program temperature control device.
Further, the inner diameter of the quartz tube is 50 mm.
Furthermore, the atmospheric pressure discharge plasma generator is of a flat plate-flat plate structure and is positioned in the quartz tube and close to one end of the air inlet tube, the atmospheric pressure discharge plasma generator comprises an upper electrode and a lower electrode which are positioned in the quartz tube and are parallel and oppositely arranged, and leads are respectively led out from the upper electrode and the lower electrode and are connected to the high-voltage power supply positioned outside the quartz tube.
Further, the upper electrode and the lower electrode are made of oxidation-resistant and heat-resistant stainless steel sheets with the length of 50mm, the width of 20mm and the thickness of 2mm, and the surfaces of the oxidation-resistant and heat-resistant stainless steel sheets are covered with Al with the purity of 99 percent2O3The ceramic is used as a medium to form a barrier layer, the length of the barrier layer is 60mm, the width of the barrier layer is 25mm, the thickness of the barrier layer is 0.5mm, and the air gap distance is 5 mm.
The precursor and the lithium source powder are uniformly mixed to form a mixture, the mixture is placed at the middle bottom of the quartz tube, and the atmospheric pressure discharge plasma generator is as close to the mixture as possible so as to fully utilize the generated plasma.
The basic principle of the invention is as follows: to reduce the cation-mixing degree in the high-nickel cathode material, the key point is to mix Ni2+Sufficient oxidation, which requires a stronger oxidizing atmosphere. Such as a roasting furnaceConnecting with atmospheric pressure discharge plasma generator, passing oxygen-containing gas into the furnace through the atmospheric pressure discharge plasma generator, stripping electrons in neutral atoms or molecules under the action of high-voltage electric field to generate O with positive charge+、O2 +、O3 +Etc. active particles having an oxidizing power higher than that of oxygen (O)2) Ozone (O)3) And atomic oxygen (O) is stronger and more readily available from Ni2+In the presence of a base to extract an electron from Ni2+Oxidation to Ni3+. The plasma gas containing a large amount of oxygen active particles and remarkably improved in oxidation capacity and activity is used for effectively strengthening Ni2+And solid-phase reaction of the precursor with a lithium source, Ni can be synthesized2+And obtaining the high-nickel cathode material which is fully oxidized and has low cation mixed-arrangement degree.
The invention mainly utilizes the enhanced oxidation effect of the active oxygen particles with positive charges generated by the atmospheric pressure discharge plasma generator, which is completely different from the method of simply connecting an ozone generator on a roasting furnace, and the effect is also more obvious. The present invention is completely different from the advanced oxidation technology mainly using hydroxyl radical (. OH) in aqueous solution, in that it uses active oxygen particles with positive charges in plasma to perform intensified oxidation on solid phase reactant and promote roasting solid phase reaction. The plasma enhanced oxidation roasting method of the high-nickel cathode material of the lithium ion battery is a new idea, and no literature report is found yet.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention connects the roasting furnace with the atmospheric pressure discharge plasma generator, the oxygen-containing gas introduced into the furnace passes through the atmospheric pressure discharge plasma generator first, and is dissociated into active particles (including O) containing a large amount of oxygen+、O2 +、O3 +Etc.) of a plasma, Ni is effectively strengthened with such a gas having remarkably improved oxidizing ability and activity2+And solid-phase reaction of the precursor with a lithium source, Ni can be synthesized2+Obtaining a high-nickel anode material which is fully oxidized and has low cation mixed-arrangement degree;
(2) because the plasma reaction generates a large amount of oxygen active particles, the oxidation capacity and the oxidation speed are obviously improved, common air or oxygen-enriched air can be used during roasting, a pure oxygen atmosphere is not needed any more, the cost of oxygen production is reduced, and the requirement on the atmosphere is obviously reduced;
(3) because the plasma reaction generates a large amount of oxygen active particles, the oxidation capacity and the oxidation speed are obviously improved, lithium carbonate can be used as a lithium source during the preparation of the high nickel material, the cost of the lithium source is obviously reduced, the labor condition is greatly improved, the corrosivity is obviously reduced, and the service life of the sagger is obviously prolonged;
(4) because a large amount of oxygen active particles are generated by plasma reaction, the oxidation capacity and the oxidation speed are obviously improved, and a lithium-rich formula is not needed to be adopted to inhibit Ni2+In Li+The occupancy of the bits. Certainly, because lithium is easy to volatilize and lose at high temperature, the lithium still needs to be in a small excess amount, and the excess amount is generally 2-5%. Therefore, the using amount of the lithium source can be obviously reduced, the cost is saved, the lithium residue is reduced, the alkalinity of the material is weakened, the subsequent processing performance is improved, and the specific capacity is also improved;
(5) the invention has important significance for improving the comprehensive performance of the high-nickel anode material, and particularly has obvious effects of reducing the cation mixing degree of the high-nickel anode material, improving the cycle performance and the rate capability of the material, reducing the alkalinity of the material and improving the processing performance of the material.
Drawings
FIG. 1 is a structural diagram of a plasma enhanced oxidizing roasting apparatus according to the present invention.
The names corresponding to the respective reference numerals in the drawings: 1-a quartz tube; 2-precursor and lithium source; 3-a high voltage power supply; 4-atmospheric pressure discharge plasma generator; 5, an air inlet pipe; 6-exhaust pipe.
Detailed Description
For a better understanding of the present invention, reference is made to the following detailed description and accompanying drawings. It is to be understood that these examples are for further illustration of the invention and are not intended to limit the scope of the invention. Moreover, it should be understood that the invention is not limited to the above-described embodiments, but is capable of various modifications and changes within the scope of the invention.
The invention relates to a method for strengthening, oxidizing and roasting a high-nickel anode material of a lithium ion battery, which is characterized in that a precursor and lithium source powder are uniformly mixed and placed in a roasting device for roasting, oxygen-containing gas is continuously introduced, and the oxygen-containing gas generates active oxygen with positive charges through plasma discharge to synthesize the high-nickel anode material.
The roasting device is a quartz tube furnace with program temperature control.
The specific implementation mode is as follows:
(1) uniformly mixing the precursor and the lithium source powder, and placing the mixture in the quartz tube furnace connected with an atmospheric pressure discharge plasma generating device;
(2) introducing oxygen-containing gas into the quartz tube furnace, discharging the reacted gas from the quartz tube furnace, and keeping the gas pressure in the furnace at normal pressure in the reaction process;
(3) adjusting the voltage, frequency and power of the atmospheric pressure discharge plasma generating device to enable the oxygen-containing gas to generate plasma discharge in the quartz tube furnace to generate active oxygen;
(4) heating the quartz tube furnace, and performing heat preservation roasting to synthesize the high-nickel anode material of the lithium ion battery;
(5) and after the baking and sintering, closing the atmospheric pressure discharge plasma generating device after the furnace temperature is reduced to be below 150 ℃.
The present invention is described with reference to the plasma enhanced oxidizing roasting apparatus shown in FIG. 1:
the method for strengthening, oxidizing and roasting the high-nickel cathode material of the lithium ion battery is carried out in a plasma strengthening, oxidizing and roasting device, and the plasma strengthening, oxidizing and roasting device comprises a quartz tube furnace and an atmospheric pressure discharge plasma generating device; the quartz tube furnace comprises a quartz tube 1, an air inlet pipe 5 positioned at one end of the quartz tube 1 and an air outlet pipe 6 positioned at the other end of the quartz tube 1; the atmospheric pressure discharge plasma generating device comprises a high-voltage power supply 3 and an atmospheric pressure discharge plasma generator 4 arranged in the quartz tube furnace.
The quartz tube 1 is arranged in a quartz tube type hearth, and the quartz tube type hearth is provided with a program temperature control device.
The quartz tube 1 has an inner diameter of 50 mm.
Atmospheric pressure discharge plasma generator 4 is dull and stereotyped structure, is located inside the quartz capsule 1 and be close to the one end of intake pipe 5, atmospheric pressure discharge plasma generator 4 is including being located quartz capsule 1 is inside parallel and relative upper electrode and the bottom electrode that sets up, follows the wire is drawn forth respectively to the upper electrode with the bottom electrode, connects to and is located quartz capsule 1 is outside on the high voltage power supply 3.
The upper electrode and the lower electrode are made of antioxidant heat-resistant stainless steel sheets with the length of 50mm, the width of 20mm and the thickness of 2mm, and the surfaces of the antioxidant heat-resistant stainless steel sheets are covered with Al with the purity of 99 percent2O3The ceramic is used as a medium to form a barrier layer, the length of the barrier layer is 60mm, the width of the barrier layer is 25mm, the thickness of the barrier layer is 0.5mm, and the air gap distance is 5 mm.
The precursor and the lithium source 2 powder are uniformly mixed to form a mixture, the mixture is placed at the bottom of the middle of the quartz tube 1, and the atmospheric pressure discharge plasma generator 4 is as close to the mixture as possible, so that plasma generated by the atmospheric pressure discharge plasma generator 4 is fully utilized.
The operation principle of the plasma enhanced oxidizing roasting device is as follows: the oxygen-containing gas is introduced from the gas inlet pipe 5 at a certain flow rate, is dissociated into active oxygen through the atmospheric pressure discharge plasma generator 4, passes through the precursor and the lithium source 2, and the reacted gas is discharged from the gas outlet pipe 6.
The plasma enhanced oxidizing and roasting method of the high nickel anode material of the lithium ion battery is further explained by the detailed embodiment in combination with the device.
Example 1
Weighing 0.1mol of precursor Ni0.80Co0.15Al0.05(OH)2And 0.105mol of lithium hydroxide LiOH. H2And O, uniformly mixing the precursor and the lithium hydroxide powder, and placing the mixture in a quartz tube (in a hearth of a quartz tube furnace). Oxygen-enriched air containing 90% of oxygen is introduced into the quartz tube furnace at the flow rate of 100ml/min, and after reactionThe gas in (2) is discharged out of the quartz tube furnace, and the gas pressure in the furnace is kept at normal pressure. An AC power supply is used, the voltage of an atmospheric pressure discharge plasma generator is adjusted to 10kV, the frequency is 15kHZ, and the power is 100W, so that plasma discharge is generated in the tube by oxygen-containing gas, and active oxygen is generated. Heating the quartz tube furnace to 800 ℃ at the heating rate of 200 ℃/h, carrying out heat preservation roasting for 12h, and then naturally cooling to room temperature. In the process, active oxygen generated by plasma discharge effectively strengthens the oxidation of nickel and the solid-phase reaction of the precursor and a lithium source, and synthesizes the high-nickel cathode material lithium nickel cobalt aluminate (molecular formula LiNi)0.80Co0.15Al0.05O2Abbreviated as NCA). After the baking and sintering, the atmospheric pressure discharge plasma generator is closed when the furnace temperature is reduced to below 150 ℃.
The degree of mixed exclusion of the positive ions in the nickel cobalt lithium aluminate positive electrode material is measured to be about 0.8 percent, the pH value is 11.20, and the first coulomb efficiency (0.1C) of the button half cell is 91.0 percent; the specific capacity of the button type half cell is 205mAh/g according to 0.1C g; 1C gram specific capacity of the aluminum-shell full battery is 175mAh/g, the cycle capacity retention rate of 300 weeks is 97.5%, and the cycle capacity retention rate of 500 weeks is 95.5%.
The prepared high-nickel anode material has the advantages of small cation mixing degree, high gram specific capacity, good cycle performance and rate performance, low alkalinity, good processing performance and excellent comprehensive performance.
Example 2
With pure O2The gas replaces oxygen-enriched air containing 90 percent of oxygen, and the high nickel cathode material of the lithium nickel cobalt aluminate is synthesized under the same other conditions as the example 1. The degree of mixed exclusion of the positive ions in the nickel cobalt lithium aluminate positive electrode material is measured to be about 0.7 percent, the pH value is 11.18, and the initial coulomb efficiency (0.1C) of the button half cell is 91.8 percent; the specific capacity of the button type half cell is 205mAh/g according to 0.1C g; 1C gram specific capacity of the aluminum-shell full battery is 175mAh/g, the cycle capacity retention rate of 300 weeks is 97.6%, and the cycle capacity retention rate of 500 weeks is 95.7%.
The prepared high-nickel cathode material also has excellent comprehensive performance, and the performance is slightly superior to that of example 1 but is very close to that of example 1. Shows that under the action of plasma reinforced oxidizing roasting, the plasma generates a great amount of active oxygen, so that pure O can be achieved even if oxygen-enriched air containing 90 percent of oxygen is used2The oxidizing effect of the gas. Therefore, the high nickel anode material is prepared under the action of plasma enhanced oxidation roasting without using pure O2Gas, can reduce the cost and the harsh requirement to the gas by a lot.
Example 3
The air is used for replacing oxygen-enriched air containing 90 percent of oxygen, and the high nickel cathode material of the lithium nickel cobalt aluminate is synthesized under the other conditions in the same way as the example 1. The degree of mixed exclusion of the positive ions in the nickel cobalt lithium aluminate positive electrode material is measured to be about 2.5 percent, the pH value is 11.78, and the initial coulomb efficiency (0.1C) of the button half cell is 89.8 percent; the specific capacity of the button type half cell is 201mAh/g by 0.1C g; 1C gram of specific capacity of the aluminum-shell full battery is 165mAh/g, the cycle capacity retention rate at 300 weeks is 93.6%, and the cycle capacity retention rate at 500 weeks is 90.5%.
The prepared high-nickel cathode material also has better comprehensive performance, which is poorer than that of the high-nickel cathode material in example 1, but is closer to the high-nickel cathode material. The result shows that under the action of plasma reinforced oxidizing roasting, the plasma generates a large amount of active oxygen, so that a better oxidizing effect can be achieved even if air is used. Therefore, air can be used when the high-nickel anode material is prepared under the action of plasma enhanced oxidation roasting, and the cost and the harsh requirements on gas can be obviously reduced. However, in order to obtain a high nickel positive electrode material having more excellent performance, it is preferable to use oxygen-rich gas.
Example 4
0.0525mol of lithium carbonate Li2CO3Instead of 0.105mol of lithium hydroxide LiOH. H in example 12And O, synthesizing the high-nickel cathode material of the lithium nickel cobalt aluminate under the same other conditions as the example 1.
The degree of mixed exclusion of the positive ions in the nickel cobalt lithium aluminate positive electrode material is measured to be about 1.0 percent, the pH value is 11.40, and the first coulomb efficiency (0.1C) of the button half cell is 90.0 percent; the specific capacity of the button type half cell is 202mAh/g according to 0.1C g; 1C gram of the aluminum-shell full-cell has a specific capacity of 172mAh/g, a cycle capacity retention rate of 96.5% at 300 weeks and a cycle capacity retention rate of 94.5% at 500 weeks.
The prepared high-nickel cathode material also has excellent comprehensive performance, and the performance is slightly inferior to that of example 1 but is very close to that of the high-nickel cathode material. Shows that under the action of plasma reinforced oxidizing roasting, the plasma generates a great deal of active oxygenSo that reducing CO is produced immediately after decomposition2Lithium carbonate Li as a lithium source for gas2CO3Can also reach lithium hydroxide LiOH.H2O is an effect of a lithium source. Therefore, lithium carbonate Li can be used for preparing the high-nickel cathode material under the action of plasma enhanced oxidizing roasting2CO3The lithium source is adopted, so that the cost of the lithium source can be obviously reduced, the labor condition is improved, the corrosivity is reduced, and the service life of the saggar is prolonged.
Example 5
Weighing 0.1mol of precursor Ni0.6Co0.2Mn0.2(OH)2And 0.0525mol of lithium carbonate Li2CO3And uniformly mixing the precursor and the lithium carbonate powder, and placing the mixture in a quartz tube (in a hearth of a quartz tube furnace). Air is introduced into the quartz tube furnace at the flow rate of 50ml/min, the gas after reaction is discharged out of the quartz tube furnace, and the gas pressure in the furnace is kept at normal pressure. The voltage of the atmospheric pressure discharge plasma generating device is adjusted to be 14kV, the frequency is 1kHZ and the power is 300W by adopting a pulse power supply, so that the air generates plasma discharge in the tube to generate active oxygen. Heating the quartz tube furnace to 900 ℃ at the heating rate of 100 ℃/h, carrying out heat preservation roasting for 48h, and then naturally cooling to room temperature. In the process, active oxygen generated by plasma discharge effectively strengthens the oxidation of nickel and the solid-phase reaction of the precursor and a lithium source, and synthesizes the high-nickel cathode material lithium nickel cobalt manganese oxide (molecular formula LiNi)0.6Co0.2Mn0.2O2Type 622). After the baking and sintering, the atmospheric pressure discharge plasma generator is closed when the furnace temperature is reduced to below 150 ℃.
The degree of mixing and arranging of the cations in the lithium nickel cobalt manganese oxide positive electrode material is measured to be about 0.7%, the pH value is 11.10, and the first coulomb efficiency (0.1C) of the button half cell is 92.0%; the specific capacity of the button type half cell is 160mAh/g according to 0.1C g; 1C gram of the aluminum-shell full-cell has the specific capacity of 145mAh/g, the cycle capacity retention rate of 97.6 percent at 300 weeks and the cycle capacity retention rate of 95.8 percent at 500 weeks.
The prepared high-nickel anode material has the advantages of small cation mixing degree, high gram specific capacity (the nickel content is lower, so the capacity is lower than NCA), good cycle performance and rate capability, low alkalinity, good processability and excellent comprehensive performance.
Example 6
Weighing 0.1mol of precursor Ni0.8Co0.1Mn0.1(OH)2And 0.105mol of lithium hydroxide LiOH. H2And O, uniformly mixing the precursor and the lithium hydroxide powder, and placing the mixture in a quartz tube (in a hearth of a quartz tube furnace). Oxygen-enriched air containing 70% of oxygen is introduced into the quartz tube furnace at the flow rate of 1L/min, the gas after reaction is discharged out of the quartz tube furnace, and the gas pressure in the furnace is kept at normal pressure. An AC power supply is used, the voltage of an atmospheric pressure discharge plasma generator is adjusted to 20kV, the frequency is 25kHZ, and the power is adjusted to 200W, so that plasma discharge is generated in the tube by oxygen-containing gas, and active oxygen is generated. And (3) raising the temperature of the quartz tube furnace to 750 ℃ at the heating rate of 300 ℃/h, carrying out heat preservation roasting for 16h, and then naturally cooling to room temperature. In the process, active oxygen generated by plasma discharge effectively strengthens the oxidation of nickel and the solid-phase reaction of the precursor and a lithium source, and synthesizes the high-nickel cathode material lithium nickel cobalt manganese oxide (molecular formula LiNi)0.8Co0.1Mn0.1O2Type 811). After the baking and sintering, the atmospheric pressure discharge plasma generator is closed when the furnace temperature is reduced to below 150 ℃.
The degree of mixing and arranging of the cations in the lithium nickel cobalt manganese oxide cathode material is measured to be about 1.2%, the pH value is 11.40, and the first coulomb efficiency (0.1C) of the button half cell is 90.0%; the specific capacity of the button type half cell is 200mAh/g according to 0.1C g; 1C gram of specific capacity of the aluminum-shell full battery is 165mAh/g, the cycle capacity retention rate at 300 weeks is 95.5%, and the cycle capacity retention rate at 500 weeks is 93.6%.
The prepared high-nickel anode material has the advantages of small cation mixing degree, high gram specific capacity, good cycle performance and rate performance, low alkalinity, good processing performance and excellent comprehensive performance.
Example 7
Weighing 0.1mol of precursor Ni0.90Co0.05Mn0.05(OH)2And 0.105mol of lithium hydroxide LiOH. H2And O, uniformly mixing the precursor and the lithium hydroxide powder, and placing the mixture in a quartz tube (in a hearth of a quartz tube furnace). Oxygen-enriched air containing 80% of oxygen is introduced into the quartz tube furnace at the flow rate of 5L/min, and the reacted gas is discharged out of the quartz tube furnaceThe gas pressure in the quartz tube furnace is kept at normal pressure. The voltage of the atmospheric pressure discharge plasma generator was adjusted to 50kV, the frequency was adjusted to 50kHZ, and the power was adjusted to 1000W by using a pulse power supply, so that plasma discharge was generated in the tube by the oxygen-containing gas to generate active oxygen. Heating the quartz tube furnace to 700 ℃ at the heating rate of 400 ℃/h, keeping the temperature, roasting for 4h, and naturally cooling to room temperature. In the process, active oxygen generated by plasma discharge effectively strengthens the oxidation of nickel and the solid-phase reaction of the precursor and a lithium source, and synthesizes the high-nickel cathode material lithium nickel cobalt manganese oxide (molecular formula LiNi)0.90Co0.05Mn0.05O2). After the baking and sintering, the atmospheric pressure discharge plasma generator is closed when the furnace temperature is reduced to below 150 ℃.
The degree of mixing and arranging of the cations in the lithium nickel cobalt manganese oxide positive electrode material is measured to be about 1.8%, the pH value is 11.70, and the first coulomb efficiency (0.1C) of the button half cell is 90.0%; the specific capacity of the button type half cell is 210mAh/g according to 0.1C g; 1C gram specific capacity of the aluminum-shell full battery is 175mAh/g, the cycle capacity retention rate at 300 weeks is 94.5%, and the cycle capacity retention rate at 500 weeks is 92.8%.
The prepared high-nickel anode material has the advantages of small cation mixing degree, high gram specific capacity (high nickel content and high capacity), good cycle performance and rate capability, low alkalinity, good processability and excellent comprehensive performance.
The following comparative description is made in connection with four prior art examples:
comparative example 1
The plasma generator was turned off, and under the same conditions as in example 1, lithium nickel cobalt aluminate was synthesized as a high nickel positive electrode material.
The degree of mixed exclusion of the positive ions in the nickel-cobalt lithium aluminate positive electrode material is measured to be about 4.5%, the pH value is 11.98, and the first coulomb efficiency (0.1C) of the button half cell is 82.8%; the specific capacity of the button half cell is 190mAh/g under 0.1C g; 1C gram of specific capacity of the aluminum-shell full battery is 140mAh/g, the cycle capacity retention rate at 300 weeks is 89.1%, and the cycle capacity retention rate at 500 weeks is 80.5%.
The prepared high-nickel anode material has the advantages of large cation mixing degree, low gram specific capacity, poor cycle performance and rate capability, high alkalinity, poor processability and remarkably reduced comprehensive performance. Under the condition of no plasma enhanced oxidation roasting action, the performance of the anode material prepared by using oxygen-enriched air containing 90 percent of oxygen is poor.
Comparative example 2
The plasma generating device is closed, and oxygen-enriched air containing 90 percent of oxygen is changed into pure O2Gas, other conditions were exactly the same as in example 1, and lithium nickel cobalt aluminate was synthesized as a high nickel positive electrode material.
The degree of mixed exclusion of the positive ions in the nickel cobalt lithium aluminate positive electrode material is measured to be about 1.5 percent, the pH value is 11.58, and the initial coulomb efficiency (0.1C) of the button half cell is 88.8 percent; the specific capacity of the button type half cell is 202mAh/g according to 0.1C g; the 1C gram specific capacity of the aluminum-shell full battery is 169mAh/g, the cycle capacity retention rate at 300 weeks is 96.1%, and the cycle capacity retention rate at 500 weeks is 93.5%.
The comprehensive performance of the prepared high-nickel cathode material is obviously lower than that of the high-nickel cathode material in example 1, but is obviously better than that of the high-nickel cathode material in example 1. Using pure O without plasma-enhanced oxidizing roasting2The anode material prepared by the gas has better performance. But under the action of plasma enhanced oxidation roasting, the high-nickel cathode material with more excellent performance can be prepared even by oxygen-enriched air containing 90 percent of oxygen.
Comparative example 3
The plasma generating device is closed, oxygen-enriched air containing 90 percent of oxygen is changed into air, other conditions are completely the same as the embodiment 1, and the high nickel cathode material of the lithium nickel cobalt aluminate is synthesized.
The degree of mixed exclusion of the positive ions in the nickel cobalt lithium aluminate positive electrode material is measured to be about 9.5 percent, the pH value is 12.10, and the first coulomb efficiency (0.1C) of the button half cell is 67.5 percent; the specific capacity of the button type half cell is 150mAh/g at 0.1C g; 1 g of specific capacity of the aluminum-shell full battery is 90mAh/g, the cycle capacity retention rate is 60.1% at 300 weeks, and the cycle capacity retention rate is 50.4% at 500 weeks.
The prepared high-nickel anode material has the advantages of high cation mixing degree, low gram specific capacity, poor cycle performance and rate performance, high alkalinity, extremely poor processability and poor comprehensive performance, and cannot be used in lithium ion batteries. The use of air to make high nickel positive electrode materials is not feasible without the plasma enhanced oxidizing calcination.
Comparative example 4
The plasma generating device is closed, and oxygen-enriched air containing 90 percent of oxygen is changed into pure O2Gas and first pure O2The gas passes through an ozone generator to generate ozone, and then enters a furnace, and the other conditions are completely the same as those in the example 1, so that the high-nickel cathode material of the lithium nickel cobalt aluminate is synthesized.
The degree of mixed exclusion of the positive ions in the nickel cobalt lithium aluminate positive electrode material is measured to be about 1.4%, the pH value is 11.48, and the initial coulomb efficiency (0.1C) of the button half cell is 88.9%; the specific capacity of the button type half cell is 202mAh/g according to 0.1C g; the 1C gram specific capacity of the aluminum-shell full battery is 169mAh/g, the cycle capacity retention rate at 300 weeks is 96.3%, and the cycle capacity retention rate at 500 weeks is 93.7%.
The comprehensive performance of the prepared high-nickel cathode material is obviously lower than that of the high-nickel cathode material in the embodiment 1 and is basically consistent with that of the high-nickel cathode material in the comparative embodiment 2. Under the condition of no plasma intensified oxidation roasting action, an ozone generator is connected to the furnace, and ozone is substituted for pure O2Gas, the effect is not significant.
Therefore, the plasma enhanced oxidation roasting method has important significance for improving the comprehensive performance of the high-nickel anode material.
The above description is not intended to limit the invention, nor is the invention limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the spirit of the invention.
Claims (5)
1. A method for strengthening, oxidizing and roasting a high-nickel anode material of a lithium ion battery is characterized in that a precursor and lithium source powder are uniformly mixed and placed in a roasting device for roasting, oxygen-containing gas is continuously introduced, and the oxygen-containing gas generates active oxygen with positive charges through plasma discharge to synthesize the high-nickel anode material; the roasting device is a quartz tube furnace;
the method comprises the following steps:
(1) uniformly mixing the precursor and the lithium source powder, and placing the mixture in the quartz tube furnace connected with an atmospheric pressure discharge plasma generating device;
(2) introducing the oxygen-containing gas into the quartz tube furnace, discharging the gas after reaction from the quartz tube furnace, and keeping the gas pressure in the furnace at normal pressure in the reaction process;
(3) adjusting the voltage of the atmospheric pressure discharge plasma generating device to be 10-50 kV, the frequency to be 1-50 kHz and the power to be 100-1000W by adopting an alternating current power supply or a pulse power supply, so that the oxygen-containing gas generates plasma discharge in the quartz tube furnace to generate active oxygen;
(4) heating the quartz tube furnace, and performing heat preservation roasting to synthesize the high-nickel anode material of the lithium ion battery;
(5) and after the baking and sintering, closing the atmospheric pressure discharge plasma generating device after the furnace temperature is reduced to be below 150 ℃.
2. The method for roasting the high-nickel cathode material of the lithium ion battery by the enhanced oxidation according to claim 1, is characterized in that: in the step (1), the lithium source is one or two of lithium hydroxide and lithium carbonate.
3. The method for roasting the high-nickel cathode material of the lithium ion battery by the enhanced oxidation according to claim 1, is characterized in that: in the step (2), the oxygen-containing gas is any one of air, oxygen-enriched air and pure oxygen, and the flow rate is 0.05-5L/min.
4. The method for strengthening, oxidizing and roasting the high-nickel cathode material of the lithium ion battery according to claim 1, characterized in that: in the step (4), the heating rate is 100-400 ℃/h, the heat preservation temperature is 700-900 ℃, and the roasting time is 4-48 h.
5. The method for roasting the high-nickel cathode material of the lithium ion battery by the enhanced oxidation according to claim 1, is characterized in that: in the step (4), the lithium ion battery high-nickel anode material is LiNixM1-xO2Wherein x is more than or equal to 1.0 and more than or equal to 0.6, and M is Cone or more of o, Mn, Al, Mg, Ti, V, Cr, Fe, Cu, Zn, Sr, Y and Zr.
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